EP0329851A2 - Procédé pour la réduction de la teneur en halogène de polycarbosilanes et polysilanes - Google Patents
Procédé pour la réduction de la teneur en halogène de polycarbosilanes et polysilanes Download PDFInfo
- Publication number
- EP0329851A2 EP0329851A2 EP88121491A EP88121491A EP0329851A2 EP 0329851 A2 EP0329851 A2 EP 0329851A2 EP 88121491 A EP88121491 A EP 88121491A EP 88121491 A EP88121491 A EP 88121491A EP 0329851 A2 EP0329851 A2 EP 0329851A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- polysilanes
- polycarbosilanes
- produced according
- sic
- production
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- 229920000548 poly(silane) polymer Polymers 0.000 title claims abstract description 27
- 229920003257 polycarbosilane Polymers 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 15
- 150000002367 halogens Chemical class 0.000 title claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 12
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- -1 alkyl radical Chemical class 0.000 abstract description 6
- RMRFFCXPLWYOOY-UHFFFAOYSA-N allyl radical Chemical compound [CH2]C=C RMRFFCXPLWYOOY-UHFFFAOYSA-N 0.000 abstract 1
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical compound C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 229910052801 chlorine Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- VEJBQZZDVYDUHU-UHFFFAOYSA-N ethenyl-hydroxy-dimethylsilane Chemical compound C[Si](C)(O)C=C VEJBQZZDVYDUHU-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910004721 HSiCl3 Inorganic materials 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical class C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910003465 moissanite Inorganic materials 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 2
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910008045 Si-Si Inorganic materials 0.000 description 1
- 229910007245 Si2Cl6 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 229910006411 Si—Si Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- BUMGIEFFCMBQDG-UHFFFAOYSA-N dichlorosilicon Chemical compound Cl[Si]Cl BUMGIEFFCMBQDG-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- IOANYFLVSWZRND-UHFFFAOYSA-N hydroxy(tripropyl)silane Chemical compound CCC[Si](O)(CCC)CCC IOANYFLVSWZRND-UHFFFAOYSA-N 0.000 description 1
- FDTBETCIPGWBHK-UHFFFAOYSA-N hydroxy-dimethyl-phenylsilane Chemical compound C[Si](C)(O)C1=CC=CC=C1 FDTBETCIPGWBHK-UHFFFAOYSA-N 0.000 description 1
- AAVUAMYXJUNZMR-UHFFFAOYSA-N hydroxy-dimethyl-prop-1-enylsilane Chemical compound CC=C[Si](C)(C)O AAVUAMYXJUNZMR-UHFFFAOYSA-N 0.000 description 1
- MLPRTGXXQKWLDM-UHFFFAOYSA-N hydroxy-methyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](O)(C)C1=CC=CC=C1 MLPRTGXXQKWLDM-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JYVWRCIOZLRMKO-UHFFFAOYSA-N tributyl(hydroxy)silane Chemical compound CCCC[Si](O)(CCCC)CCCC JYVWRCIOZLRMKO-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 1
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
- C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
Definitions
- the invention relates to a process for reducing the halogen content of polycarbosilanes and / or polysilanes containing halogen bonded directly to silicon atoms.
- Polysilanes and polycarbosilanes are valuable intermediates for the production of silicon carbide.
- Polysilanes for example, can be prepared from organochlorodisilanes in the presence of tetraalkylphosphonium or tetraalkylammonium halides (US Pat. No. 4,298,558, GB 2,024,789). Because of this production method, the polymers mentioned contain considerable amounts of chlorine bonded to silicon atoms. In order to prevent the release of halogen-containing gases during the further processing of the polymers into silicon carbide, this halogen content must be reduced. RH Baney et al.
- the object of the present invention was to provide a process for reducing the halogen content of halogen-containing polysilanes and polycarbosilanes, which is simple in terms of equipment, the reagent used being inexpensive and without major safety precautions, and unwanted products and excess reagent according to the let the process underlying the reaction be removed in a simple manner.
- This object is achieved by the present invention in that said polysilanes and / or polycarbosilanes with compounds of the general formula R3SiOH, where R is independently hydrogen, alkyl radical having 1 to 10 carbon atoms, vinyl, allyl or phenyl radical are brought into contact.
- Examples of compounds of the general formula R3SiOH are trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, triphenylsilanol, dimethylvinylsilanol, dimethylpropenylsilanol, dimethylphenylsilanol and diphenylmethylsilanol.
- Preferred compounds used according to the invention are trimethylsilanol and dimethylvinylsilanol.
- Polysilanes containing halogen bonded directly to silicon atoms are known, for example, from the literature cited at the beginning. They are made up of units of the formula R1 n Si (I) built up, with R1 identical or different halogen and / or hydrocarbon radicals with 1 to 18 carbon atoms, especially the chlorine atom and / or the methyl radical; n is an integer of 0, 1, 2, or 3 means, and the units are linked via Si-Si bonds.
- Halogen-containing polycarbosilanes bonded directly to silicon atoms are also known; their production is described, for example, in W. Noll, Chemistry and Technology of Silicones, Academic Press, Orlando, 1968, pages 356-364. They are made up of units of the formula (R1 n Si-R2 3-n ⁇ (II) l constructed, wherein R1 and n have the meanings given above for formula (I), and R2 are divalent hydrocarbon radicals having 1 to 18 carbon atoms, in particular phenylene radicals and radicals of the formula - (CH2) m -, where m is an integer from 1 to 8.
- Such polycarbosilanes include accessible by the reaction of dimethyldichlorosilane with 1,6-dichlorohexane (ibid, p. 357).
- the process according to the invention can of course be applied to all polymers which contain halogen atoms bonded directly to silicon atoms.
- Such can also be prepared, for example, by pyrolysis of alkylchlorosilanes at 400-700 ° C or by passing HSiCl3 over them, SiCl4 or Si2Cl6 over heated to 1000 - 1300 ° C silicon.
- polysilanes and / or polycarbosilanes mentioned at the beginning and in the main claim also includes those polymers which carry both units of the formula (I) and those of the formula (II) in one molecule. Mixtures of polysilanes, mixtures of polycarbosilanes and mixtures of at least one polysilane with at least one polycarbosilane are also to be counted under this term.
- the process according to the invention is preferably carried out at temperatures from 20 ° C. to 300 ° C., in particular from 50 ° C. to 200 ° C.
- the above reaction can be carried out at ambient pressure, i.e. 0.102 MPa (abs.) Or about 0.102 MPa (abs.), But it can also be carried out at higher or lower pressures. Pressures from 0.01 MPa to 2 MPa (abs.) Are preferred.
- the reaction time is preferably 0.1 h to 10 h, in particular 1 h to 5 h.
- the process according to the invention can be carried out with the addition of an inert solvent.
- solvents are aromatics and substituted aromatics, such as Benzene, toluene; aliphatic hydrocarbons and their mixtures, such as n-octane, n-decane, octane isomer genetics, petroleum ether of various boiling ranges and the like.
- ethers such as diethyl ether, diisopropyl ether, di-n-butyl ether, THF or dioxane.
- the process according to the invention is preferably carried out in the presence of a base, in particular in the presence of a compound containing a basic nitrogen.
- the bases are preferably used in excess or in equimolar amounts to the amount equivalent to the chlorine to be removed.
- Examples of basic nitrogen-containing compounds are primary, secondary and tertiary amines, urea, heterocycles such as pyridine, pyrrole, pyrrolidine, imidazole, quinoline, quinazoline, quinoxaline, s-triazine, 1,2,4-triazole.
- trimethylamine triethylamine, tri-n-butylamine, pyridine, picoline, collidine, N, N-dimethylaniline, N, N-diethylaniline, 1,4-diazabicyclo (2,2,2) octane and 1,8-diazabicyclo ( 5,4,0) undec-7-en, use.
- the polysilanes and / or polycarbosilanes produced according to the invention are used according to methods known per se for producing SiC, such as SiC-containing ceramic material, SiC fibers or SiC-containing ceramic protective layers. An overview of such processes is described by R. West in the Journal of Organometallic Chemistry 300, 327-346 (1986).
- the polysilane and / or polycarbosilane obtained according to the invention is pyrolyzed in an inert atmosphere or in a vacuum at temperatures from 700 ° to 1300 ° C.
- polysilanes and / or polycarbosilanes produced according to the invention are also used as binders in the sintering of, for example, SiC, Si3N4, B4C, BN, TiC, TiN.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
- Inorganic Fibers (AREA)
- Ceramic Products (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3743595 | 1987-12-22 | ||
| DE19873743595 DE3743595A1 (de) | 1987-12-22 | 1987-12-22 | Verfahren zur verringerung des halogengehaltes von halogenhaltigen polycarbosilanen und polysilanen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0329851A2 true EP0329851A2 (fr) | 1989-08-30 |
| EP0329851A3 EP0329851A3 (fr) | 1990-10-17 |
Family
ID=6343304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19880121491 Withdrawn EP0329851A3 (fr) | 1987-12-22 | 1988-12-22 | Procédé pour la réduction de la teneur en halogène de polycarbosilanes et polysilanes |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0329851A3 (fr) |
| JP (1) | JPH01203428A (fr) |
| DE (1) | DE3743595A1 (fr) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE68921884T2 (de) * | 1988-12-29 | 1995-08-10 | Canon Kk | Polysilanverbindung und daraus hergestellter elektrophotographischer photorezeptor. |
| DE4039519A1 (de) * | 1989-12-11 | 1991-06-13 | Canon Kk | Sperrschicht-photoelement mit einer aus einer polysilanverbindung gebildeten organischen halbleiterschicht |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0000993B1 (fr) * | 1977-08-22 | 1982-12-08 | Imperial Chemical Industries Plc | Procédé pour la production d'ammoniac |
| US4310481A (en) * | 1980-07-23 | 1982-01-12 | Dow Corning Corporation | High yield silicon carbide pre-ceramic polymers |
-
1987
- 1987-12-22 DE DE19873743595 patent/DE3743595A1/de not_active Withdrawn
-
1988
- 1988-12-21 JP JP63320792A patent/JPH01203428A/ja active Pending
- 1988-12-22 EP EP19880121491 patent/EP0329851A3/fr not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01203428A (ja) | 1989-08-16 |
| EP0329851A3 (fr) | 1990-10-17 |
| DE3743595A1 (de) | 1989-07-13 |
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